Fluorenonylamino anthraquinone acid dyestuffs



fatenteci Aug. 14 i5i V i FL I'JORENONYLAMINO ANTHRAQUINONE 3 ACID DYESTUFFS Ci rt G. Vogt, Union, N. .L, assignor to General Aniline- &-Fil'm Corporation, New York, N. Y., a corporation of Delaware I NoDrawing. Application December 17, 1947, H I ,Serial No. 792,351

-' 4 Claims. (01. 2600-374);

The present inventionrelatesto new comthe sulf'onicacid group or groupsenter into the pounds of the anthraquinone series, more parbe nz nuclei of the fluorenonyl radicalfof 'fthe ticularly to new greenish-blue acid dyestuffs of compounds. The 'sulfonated dyestuffs as thefr'ee the general formula: acidfor in theformof the alkali metal cram? 5 monium salts have good levelling properties and dye animal and nylon fibers from neutraf'or acid bath in greenish blue shades of good fast- ;ness to light, washing and crocking. The alkaliinetal and. ammonium saltsofQthe dyestuffs can be prepared in known Way byTrefacting the free acid of the dyestuff with an'aqueous solution of .an equivalent weight of caustic alkali, e. g., sodium hydroxide, or of a monia. By heating the salt of the dyestuff in dilute aqueand the alkah: metal and ammmum salts sous hydrochloric acid,',the dyestuff is precipitated as the free acid and can be. collected y" filtration.

The dyestuifs of the above formula contain The capacity of-the new compoundsvtor dye sum) 9 2'posmon of the anthraiquinone animal and nylon fibers from neutral bath nucleus and in the form of the free acid or as a very aluable p r qp erty for the uni d e the alkali !"Q F P J are of textiles Where sne r the 'fibers'is 'sens'itive'to Pounds of F llmlted S1E1b111tY111,Water- They' the action of acids. For example, in' the dyeing be apphed. to the q t fm or W 9 from neutral bath of mixed fibers of wool and ?m d b m m ,oflaqtleolls cotton or of nylon andcctton with a dyestuff dispersions 'ina suitablelamedium such as lignin of the invention the woolxandknylon is in each sodmmsulfonftte- The compoueds F Wl-9 case dyed a greenish blue 'shade whereas the nylon from and or u a h m sh blue cotton, which remains undyed, is not tendered shades of goodiastness 9 1 51 it and as would occur on using an .acid bath for the mocking these i ls iq eri bemg the dyeing. A preferred group of the compounds Stronger in the nylon for use in neutral bath dyeing are the ammonium The w dyestufis can'bieiohtalped by i' salts because of the nearly neutral character of mg 1'amlno'4halogen'anthmqumoneiz'sulfomc the aqueous solutions thereof which can be obacid (halogen may be chlorine or bromine) or vmined with water; v h i a @the alkali metal or ammonium Sal-ts thereof with The invention is further.fillustratedabylthe the correspondmg fiuofenoneamme' whlch may following examples to which, however, it is not be or 9 The intended that it be limited. Parts are by weight.

densation is carried out by heating an aqueous 3o solution of the 1-amino-4-halogen anthraqui- Example 1 none-2-sulfonic acid or of a salt thereof in admixture with a solution of the fiuorenoneamine in A mlxture parts of sodmm f' a. water-miscible organic solvent such as ethanol bmm9anthraqumne'z'sulfonfitet Parts sodl" in the presence of a catalyst for the condensa- 40 um blcarbonatefifi parts 8961mm carbonate and 500 parts water is charged into a reaction vessel tion such as copper or a copper salt and an acid binding agent Such as Sodium or potassium bicar equipped with a stirrer, thermometer and reflux bonate, To insure obtaining the product in the condenser. TO this mixture at 80 C. is added a highest state of purity, the reaction is preferably suspension of 23.4 parts Z-aminofluorenone in carried out with exclusion of air from the hot 245 par ethanol and 2 CHDIOIIS Chloride he reaction mixture. This may be accomplished by mixture is maintained with stirring at gentle conducting the reaction in an atmosphere of an reflllX for h A Sample Viewed W h the inert gas such as nitrogen or carbon dioxide or w p r mi s p sh ws ma y fine r nish mm blue needles. The reaction mixture is filtered Th dyestuffs ma be sulfonated to in rea e and the cake dispersed in 1000 parts of hot wate r. their solubility in water by treatment with oleum At C. is added parts hy oc lor c mud or concentrated sulfuric acid. From 1 to 3 sul- (10% by Weight). The precipitate which forms fonic acid groups are introduced, depending on is collected by filtration. The cake is reslurned the number of reactive positions available in and again precipitated by essentially the same the molecule of the compounds. Most probably 65 procedure. The cake is washed with water, A

3 portion evaporated to dryness with ammonium hydroxide yields a product which dyes nylon well from the neutral or acid bath in attractive blue shades of good fastness and has the probable formula:

Example 2 Four parts of the dried cake from Example 1 are pulverized and sulfonated by stirring with 70 parts 20% oleum for fifteen minutes at 50 C. The solution is poured over 200' parts ice. The dyestuff, which is' freely soluble is precipitated by th addition of ammonium hydroxide: and salt. The product dyes wool and nylon in attractive Tblue shades of good light fastness.

Example 3;

A portion of'thepaste from Example 1 is milled to dryness in the werner Pfleiderer'mill with an 'equal' weight (based on the dry content of the pastel of a dispersing agent which essentially is lignin sodium sulfonate. The resultant dispersed material colors nylon attractive blue shades of good strength, from either the neutral or acid bath. The dyeings show good fastness to-wash- 'ing and have excellent fastness to light inboth heavy and light shades.

, I claim:

I. An anthraquinone compound selected from the group consisting of the free acid of the formula:

and the alkali metal and ammonium salts thereof.

2. An anthraquinone compound, selected. from the group consisting of the free acid of the formula:

O NH,

. soar and the alkali metal and ammonium salts thereof.

3. An anthraquinone compound of the formula:

4. The anthraquinone compound of the formula:

The following references. are of record in. the file of this patent: v

UNITED STATES; PATENTS" Number Name Date 2,113,231 Deinet Apr. 5; 1938 2369;969 Lulek et a1. Feb; 20, 1-945 FOREIGN PATENTS Humber Country I Date I 7,632 Great Britain Dec. 1, 1910 269,194 Germany Jan. 13, 1914 568.567 Germany Jan. 20; 198 3 

1. AN ANTHRAQUINONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE FREE ACID OF THE FORMULA: 